Soft magnetic alloy and magnetic device

ABSTRACT

A soft magnetic alloy includes a main component of (Fe(1−(α+β))X1αX2β)(1−(a+b+c+d+e))MaBbPcSidCe. X1 is one or more of Co and Ni. X2 is one or more of Al, Mn, Ag, Zn, Sn, As, Sb, Cu, Cr, Bi, N, O, and rare earth elements. M is one or more of Nb, Hf, Zr, Ta, Mo, W, and V. 0.020≤a≤0.14 is satisfied. 0.020&lt;b≤0.20 is satisfied. 0≤d≤0.060 is satisfied. α≥0 is satisfied. β≥0 is satisfied. 0≤α+β≤0.50 is satisfied. c and e are within a predetermined range. The soft magnetic alloy has a nanohetero structure or a structure of Fe based nanocrystallines.

BACKGROUND OF THE INVENTION

The present invention relates to a soft magnetic alloy and a magneticdevice.

Low power consumption and high efficiency have been demanded inelectronic, information, communication equipment, and the like.Moreover, the above demands are becoming stronger for a low carbonsociety. Thus, reduction in energy loss and improvement in power supplyefficiency are also required for power supply circuits of electronic,information, communication equipment, and the like. Then, improvement insaturation magnetic flux density and permeability and reduction in coreloss (magnetic core loss) are required for the magnetic core of themagnetic element used in the power supply circuit. The reduction in coreloss reduces the loss of power energy, and the improvement inpermeability downsizes a magnetic element. Thus, high efficiency andenergy saving are achieved.

Patent Document 1 discloses a Fe—B-M based soft magnetic amorphous alloy(M=Ti, Zr, Hf, V, Nb, Ta, Mo, and W). This soft magnetic amorphous alloyhas favorable soft magnetic properties, such as a high saturationmagnetic flux density, compared to a saturation magnetic flux density ofa commercially available Fe based amorphous material.

Patent Document 1: JP3342767 (B2)

BRIEF SUMMARY OF INVENTION

As a method of reducing the core loss of the magnetic core, it isconceivable to reduce coercivity of a magnetic material constituting themagnetic core.

Patent Document 1 discloses that soft magnetic characteristics can beimproved by depositing fine crystal phases in the Fe based soft magneticalloy. At present, however, required is a soft magnetic alloy havinghigh soft magnetic characteristics and being capable of maintaining ahigh permeability to a higher frequency.

It is an object of the invention to provide a soft magnetic alloy havinghigh resistivity and saturation magnetic flux density and a lowcoercivity and being capable of maintaining a high permeability to ahigher frequency.

To achieve the above object, a soft magnetic alloy according to thefirst aspect of the present invention includes a main component of(Fe_((1−(α+β)))X1_(α)X2_(β))_((1−(a+b+c+d+e)))M_(a)B_(b)P_(c)Si_(d)C_(e),in which

-   -   X1 is one or more of Co and Ni,    -   X2 is one or more of Al, Mn, Ag, Zn, Sn, As, Sb, Cu, Cr, Bi, N,        O, and rare earth elements,

M is one or more of Nb, Hf, Zr, Ta, Mo, W, and V,

0.020≤a≤0.14 is satisfied,

0.020<b≤0.20 is satisfied,

0.040<c≤0.15 is satisfied,

0≤d≤0.060 is satisfied,

0≤e≤0.030 is satisfied,

α≥0 is satisfied,

β≥0 is satisfied, and

0≤α+β≤0.50 is satisfied,

wherein the soft magnetic alloy has a nanohetero structure where initialfine crystals exist in an amorphous phase.

To achieve the above object, a soft magnetic alloy according to thesecond aspect of the present invention includes a main component of(Fe_((1−(α+β)))X1_(α)X2_(β))_((1−(a+b+c+d+e)))M_(a)B_(b)P_(c)Si_(d)C_(e),in which

X1 is one or more of Co and Ni,

X2 is one or more of Al, Mn, Ag, Zn, Sn, As, Sb, Cu, Cr, Bi, N, O, andrare earth elements,

M is one or more of Nb, Hf, Zr, Ta, Mo, W, and V,

0.020≤a≤0.14 is satisfied,

0.020<b≤0.20 is satisfied,

0<c≤0.040 is satisfied,

0≤d≤0.060 is satisfied,

0.0005<e<0.0050 is satisfied,

α≥0 is satisfied,

β≥0 is satisfied, and

0≤α+β≤0.50 is satisfied,

wherein the soft magnetic alloy has a nanohetero structure where initialfine crystals exist in an amorphous phase.

In the soft magnetic alloy according to the first and second aspects ofthe present invention, the initial fine crystals may have an averagegrain size of 0.3 to 10 nm.

To achieve the above object, a soft magnetic alloy according to thethird aspect of the present invention includes a main component of(Fe_((1−(α+β)))X1_(α)X2_(β))_((1−(a+b+c+d+e)))M_(a)B_(b)P_(c)Si_(d)C_(e),in which

X1 is one or more of Co and Ni,

X2 is one or more of Al, Mn, Ag, Zn, Sn, As, Sb, Cu, Cr, Bi, N, O, andrare earth elements,

M is one or more of Nb, Hf, Zr, Ta, Mo, W, and V,

0.020≤a≤0.14 is satisfied,

0.020<b≤0.20 is satisfied,

0.040<c≤0.15 is satisfied,

0≤d≤0.060 is satisfied,

0≤e≤0.030 is satisfied,

α≥0 is satisfied,

β≥0 is satisfied, and

0≤α+β≤0.5 is satisfied,

wherein the soft magnetic alloy has a structure of Fe basednanocrystallines.

To achieve the above object, a soft magnetic alloy according to thefourth aspect of the present invention includes a main component of(Fe_((1−(α+β)))X1_(α)X2_(β))_((1−(a+b+c+d+e)))M_(a)B_(b)P_(c)Si_(d)C_(e),in which

X1 is one or more of Co and Ni,

X2 is one or more of Al, Mn, Ag, Zn, Sn, As, Sb, Cu, Cr, Bi, N, O, andrare earth elements,

M is one or more of Nb, Hf, Zr, Ta, Mo, W, and V,

0.020≤a≤0.14 is satisfied,

0.020<b≤0.20 is satisfied,

0<c≤0.040 is satisfied,

0≤d≤0.060 is satisfied,

0.0005<e<0.0050 is satisfied,

α≥0 is satisfied,

β≥0 is satisfied, and

0≤α+β≤0.50 is satisfied,

wherein the soft magnetic alloy has a structure of Fe basednanocrystallines.

In the soft magnetic alloy according to the third and fourth aspects ofthe present invention, the Fe based nanocrystallines may have an averagegrain size of 5 to 30 nm.

Since the soft magnetic alloy according to the first aspect of thepresent invention has the above features, the soft magnetic alloyaccording to the third aspect of the present invention is easilyobtained by heat treatment. Since the soft magnetic alloy according tothe second aspect of the present invention has the above features, thesoft magnetic alloy according to the fourth aspect of the presentinvention is easily obtained by heat treatment. In the soft magneticalloy according to the third aspect and the soft magnetic alloyaccording to the fourth aspect, a high resistivity, a high saturationmagnetic flux density, and a low coercivity can be achieved at the sametime, and a higher permeability μ′ can be maintained to a higherfrequency. Incidentally, μ′ is a real part of a complex permeability.

The following description regarding the soft magnetic alloys accordingto the present invention is common among the first to fourth aspects.

In the soft magnetic alloys according to the present invention,0.73≤1−(a+b+c+d+e)≤0.95 may be satisfied.

In the soft magnetic alloys according to the present invention,0≤α{1−(a+b+c+d+e)}≤0.40 may be satisfied.

In the soft magnetic alloys according to the present invention, α=0 maybe satisfied.

In the soft magnetic alloys according to the present invention,0≤β{1−(a+b+c+d+e)}≤0.030 may be satisfied.

In the soft magnetic alloys according to the present invention, β=0 maybe satisfied.

In the soft magnetic alloys according to the present invention, α=β=0may be satisfied.

The soft magnetic alloys according to the present invention may have aribbon shape.

The soft magnetic alloys according to the present invention may have apowder shape.

A magnetic device according to the present invention contains theabove-mentioned soft magnetic alloy.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a schematic view of a single roller method.

FIG. 2 is a schematic view of a single roller method.

DETAILED DESCRIPTION OF INVENTION

Hereinafter, First Embodiment to Fifth Embodiment of the presentinvention are explained.

First Embodiment

A soft magnetic alloy according to the present embodiment includes amain component of(Fe_((1−(α+β)))X1_(α)X2_(β))_((1−(a+b+c+d+e)))M_(a)B_(b)P_(c)Si_(d)C_(e),in which

X1 is one or more of Co and Ni,

X2 is one or more of Al, Mn, Ag, Zn, Sn, As, Sb, Cu, Cr, Bi, N, O, andrare earth elements,

M is one or more of Nb, Hf, Zr, Ta, Mo, W, and V,

0.020≤a≤0.14 is satisfied,

0.020<b≤0.20 is satisfied,

0.040<c≤0.15 is satisfied,

0≤d≤0.060 is satisfied,

0≤e≤0.030 is satisfied,

α≥0 is satisfied,

β≥0 is satisfied, and

0≤α+β≤0.50 is satisfied,

wherein the soft magnetic alloy has a nanohetero structure where initialfine crystals exist in an amorphous phase.

When the above-mentioned soft magnetic alloy (a soft magnetic alloyaccording to the first aspect of the present invention) undergoes a heattreatment, Fe based nanocrystallines are easily deposited in the softmagnetic alloy. In other words, the above-mentioned soft magnetic alloyeasily becomes a starting raw material of a soft magnetic alloy where Febased nanocrystallines are deposited (a soft magnetic alloy according tothe third aspect of the present invention). Incidentally, the initialfine crystals preferably have an average grain size of 0.3 to 10 nm.

The soft magnetic alloy according to the third aspect of the presentinvention includes the same main component as the soft magnetic alloyaccording to the first aspect and a structure of Fe basednanocrystallines.

The Fe based nanocrystallines are crystals whose grain size isnano-order and whose crystal structure of Fe is bcc (body-centeredcubic). In the present embodiment, it is preferable to deposit Fe basednanocrystallines having an average grain size of 5 to 30 nm. The softmagnetic alloy where Fe based nanocrystallines are deposited is easy tohave a high saturation magnetic flux density and a low coercivity.

Hereinafter, each component of the soft magnetic alloy according to thepresent embodiment is explained in detail.

M is one or more of Nb, Hf, Zr, Ta, Mo, W, and V.

The M content (a) satisfies 0.020≤a≤0.14. The M content (a) ispreferably 0.040≤a≤0.10, more preferably 0.050≤a≤0.080. When the Mcontent (a) is small, a crystal phase composed of crystals having agrain size of larger than 30 nm is easily generated in the soft magneticalloy. When the crystal phase is generated, Fe based nanocrystallinescannot be deposited by heat treatment, and the soft magnetic alloyeasily has a low resistivity, a high coercivity, and a low permeabilityμ′. When the M content (a) is large, the soft magnetic alloy easily hasa low saturation magnetic flux density.

The B content (b) satisfies 0.020<b≤0.20. The B content (b) may be0.025≤b≤0.20 and is preferably 0.060≤b≤0.15, more preferably0.080≤b≤0.12. When the B content (b) is small, a crystal phase composedof crystals having a grain size of larger than 30 nm is easily generatedin the soft magnetic alloy. When the crystal phase is generated, Febased nanocrystallines cannot be deposited by heat treatment, and thesoft magnetic alloy easily has a low resistivity, a high coercivity, anda low permeability μ′. When the B content (b) is large, the softmagnetic alloy easily has a low saturation magnetic flux density.

The P content (c) satisfies 0.040<c≤0.15. The P content (c) may be0.041≤c≤0.15 and is preferably 0.045≤c≤0.10, more preferably0.050≤c≤0.070. When the P content (c) is in the above range, especiallyin the range of c>0.040, the soft magnetic alloy has an improvedresistivity and a low coercivity. Moreover, when the soft magnetic alloyhas an improved resistivity, a high permeability μ′ can be maintained toa higher frequency. When the P content (c) is small, the above effectsare hard to be obtained. When the P content (c) is large, the softmagnetic alloy easily has a low saturation magnetic flux density.

The Si content (d) satisfies 0≤d≤0.060. That is, Si may not becontained. The Si content (d) is preferably 0.005≤d≤0.030, morepreferably 0.0104≤d≤0.020. When the soft magnetic alloy contains Si,resistivity is particularly easily improved, and coercivity is easilydecreased. Moreover, when the soft magnetic alloy has an improvedresistivity, a high permeability μ′ can be maintained to a highfrequency. When the Si content (d) is large, the soft magnetic alloy hasan increased coercivity on the contrary.

The C content (e) satisfies 0≤e≤0.030. That is, C may not be contained.The C content (e) is preferably 0.001≤e≤0.010, more preferably0.001≤e≤0.005. When the soft magnetic alloy contains C, coercivity isparticularly easily decreased, and coercivity is easily decreased. Whenthe C content (e) is large, the soft magnetic alloy has a lowresistivity and has an increased coercivity on the contrary, and a highpermeability μ′ is hard to be maintained to a high frequency.

The Fe content (1−(a+b+c+d+e)) is not limited, but is preferably0.73≤(1−(a+b+c+d+e))≤0.95. When the Fe content (1−(a+b+c+d+e)) is in theabove range, a crystal phase composed of crystals having a grain size oflarger than 30 nm is hard to be generated, and it thereby becomes easyto obtain a soft magnetic alloy where Fe based nanocrystallines aredeposited.

In the soft magnetic alloy according to the present embodiment, a partof Fe may be substituted by X1 and/or X2.

X1 is one or more of Co and Ni. The X1 content may be α=0. That is, X1may not be contained. Preferably, the number of atoms of X1 is 40 at %or less if the number of atoms of the entire composition is 100 at %.That is, 0≤α{1−(a+b+c+d+e)}≤0.40 is preferably satisfied.

X2 is one or more of Al, Mn, Ag, Zn, Sn, As, Sb, Cu, Cr, Bi, N, O, andrare earth elements. The content X2 may be β=0. That is, X2 may not becontained. Preferably, the number of atoms of X2 is 3.0 at % or less ifthe number of atoms of the entire composition is 100 at %. That is,0≤β{1−(a+b+c+d+e)}≤0.030 is preferably satisfied.

The substitution amount of Fe by X1 and/or X2 is half or less of Febased on the number of atoms. That is, 0≤α+β≤0.50 is satisfied. Whenα+β>0.50 is satisfied, the soft magnetic alloy according to the thirdaspect of the present invention is hard to be obtained by heattreatment.

Incidentally, the soft magnetic alloys of the present embodiment maycontain elements other than the above-mentioned elements as unavoidableimpurities. For example, 0.1 wt % or less of unavoidable impurities maybe contained with respect to 100 wt % of the soft magnetic alloy.

Hereinafter, a method of manufacturing the soft magnetic alloy isexplained.

The soft magnetic alloy is manufactured by any method. For example, aribbon of the soft magnetic alloy is manufactured by a single rollermethod. The ribbon may be a continuous ribbon.

In the single roller method, pure metals of respective metal elementscontained in a soft magnetic alloy finally obtained are initiallyprepared and weighed so that a composition identical to that of the softmagnetic alloy finally obtained is obtained. Then, the pure metal ofeach metal element is melted and mixed, and a base alloy is prepared.Incidentally, the pure metals are melted by any method. For example, thepure metals are melted by high-frequency heating after a chamber isevacuated. Incidentally, the base alloy and the soft magnetic alloyfinally obtained normally have the same composition.

Next, the prepared base alloy is heated and melted, and a molten metalis obtained. The molten metal has any temperature, and may have atemperature of 1200 to 1500° C., for example.

FIG. 1 is a schematic view of an apparatus used for a single rollermethod according to the present embodiment. In the single roller methodaccording to the present embodiment, a molten metal 22 is sprayed andsupplied from a nozzle 21 against a roller 23 rotating in the arrowdirection, and a ribbon 24 is thereby manufactured in the rotatingdirection of the roller 23 in a chamber 25. Incidentally, the roller 23is made by any material, such as Cu, in the present embodiment.

On the other hand, FIG. 2 is a schematic view of an apparatus used for anormally employed single roller method. In a chamber 35, a molten metal32 is sprayed and supplied from a nozzle 31 against a roller 33 rotatingin the arrow direction, and a ribbon 34 is manufactured in the rotatingdirection of the roller 33.

In the single roller method, it is conventionally considered that amolten metal is preferably cooled rapidly by increasing a cooling rate,that the cooling rate is preferably increased by increasing a contacttime between the molten metal and a roller and by increasing atemperature difference between the molten metal and the roller, and thatthe roller thereby preferably normally has a temperature of about 5 to30° C.

The present inventors can achieve a rapid cooling of the ribbon 24 evenif the roller 23 has a high temperature of about 50 to 70° C. byrotating the roller 23 in the opposite direction (see FIG. 1) to thenormal direction so as to further increase a contact time between theroller 23 and the ribbon 24. The soft magnetic alloy with thecomposition according to First Embodiment has a high uniformity of thecooled ribbon 24 and has fewer crystal phases composed of crystalshaving a grain size of larger than 30 nm by increasing the temperatureof the roller 23 and further increasing a contact time between theroller 23 and the ribbon 24 compared to prior arts. In spite of acomposition where crystals having a grain size of larger than 30 nm aregenerated in a conventional method, it is consequently possible toobtain a soft magnetic alloy containing no crystal phases composed ofcrystals having a grain size of larger than 30 nm. Incidentally, whenthe roller has a normal temperature of 5 to 30° C. while being rotatedin the opposite direction (see FIG. 1) to the normal direction, theribbon 24 is easily peeled from the roller 23, and the effect of theopposite rotation cannot be obtained.

In the single roller method, the thickness of the ribbon 24 to beobtained can be controlled by mainly controlling the rotating speed ofthe roller 23, but can also be controlled by, for example, controllingthe distance between the nozzle 21 and the roller 23, the temperature ofthe molten metal, and the like. The ribbon 24 has any thickness. Forexample, the ribbon 24 may have a thickness of 15 to 30 μm.

The chamber 25 has any inner vapor pressure. For example, the chamber 25may have an inner vapor pressure of 11 hPa or less using an Ar gas whosedew point is adjusted. Incidentally, the chamber 25 has no lower limitfor inner vapor pressure. The chamber 25 may have a vapor pressure of 1hPa or less by being filled with an Ar gas whose dew point is adjustedor by being turned into a state close to vacuum.

The ribbon 24 (soft magnetic alloy according to the present embodiment)contains an amorphous phase containing no crystals having a grain sizeof larger than 30 nm and has a nanohetero structure where initial finecrystals exist in the amorphous phase. When the soft magnetic alloyundergoes the following heat treatment, Fe based nanocrystallines areeasily deposited.

Incidentally, any method, such as a normal X-ray diffractionmeasurement, can be used for confirming whether the ribbon 24 containscrystals having a grain size of larger than 30 nm.

The existence and average grain size of the above-mentioned initial finecrystals are observed by any method, and can be observed by, forexample, obtaining a selected area electron diffraction image, a nanobeam diffraction image, a bright field image, or a high resolution imageusing a transmission electron microscope with respect to a samplethinned by ion milling. When using a selected area electron diffractionimage or a nano beam diffraction image, with respect to diffractionpattern, a ring-shaped diffraction is formed in case of being amorphous,and diffraction spots due to crystal structure are formed in case ofbeing non-amorphous. When using a bright field image or a highresolution image, an existence and an average grain size of initial finecrystals can be confirmed by visual observation with a magnification of1.00×10⁵ to 3.00×10⁵.

The roller has any temperature and rotating speed, and the chamber hasany atmosphere. Preferably, the roller has a temperature of 4 to 30° C.for amorphization. The faster a rotating speed of the roller is, thesmaller an average grain size of initial fine crystals is. Preferably,the roller has a rotating speed of 25 to 30 m/sec. for obtaining initialfine crystals having an average grain size of 0.3 to 10 nm. In view ofcost, the chamber preferably has an atmosphere air.

Hereinafter, explained is a method of manufacturing a soft magneticalloy having a structure of Fe based nanocrystallines (a soft magneticalloy according to the third aspect of the present invention) bycarrying out a heat treatment against a ribbon 24 composed of a softmagnetic alloy having a nanohetero structure (a soft magnetic alloyaccording to the first aspect of the present invention).

The soft magnetic alloy according to the present embodiment ismanufactured with any heat-treatment conditions. Favorableheat-treatment conditions differ depending on a composition of the softmagnetic alloy. Normally, a heat-treatment temperature is preferablyabout 450 to 650° C., and a heat-treatment time is preferably about 0.5to 10 hours, but favorable heat-treatment temperature and heat-treatmenttime may be in a range deviated from the above ranges depending on thecomposition. The heat treatment is carried out in any atmosphere, suchas an active atmosphere of air and an inert atmosphere of Ar gas.

Any method, such as observation using a transmission electronmicroscope, is employed for calculation of an average grain size of Febased nanocrystallines contained in the soft magnetic alloy obtained byheat treatment. The crystal structure of bcc (body-centered cubicstructure) is also confirmed by any method, such as X-ray diffractionmeasurement.

In addition to the above-mentioned single roller method, a powder of thesoft magnetic alloy according to the present embodiment is obtained by awater atomizing method or a gas atomizing method, for example.Hereinafter, a gas atomizing method is explained.

In a gas atomizing method, a molten alloy of 1200 to 1500° C. isobtained similarly to the above-mentioned single roller method.Thereafter, the molten alloy is sprayed in a chamber, and a powder isprepared.

At this time, the above-mentioned favorable nanohetero structure isobtained easily with a gas spray temperature of 50 to 200° C. and avapor pressure of 4 hPa or less in the chamber.

After the powder composed of the soft magnetic alloy having thenanohetero structure is prepared by the gas atomizing method, a heattreatment is conducted at 400 to 600° C. for 0.5 to 10 minutes. Thismakes it possible to promote diffusion of atoms while the powder isprevented from being coarse due to sintering of each grain, reach athermodynamic equilibrium state for a short time, remove distortion andstress, and easily obtain a Fe based soft magnetic alloy having anaverage grain size of 10 to 50 nm.

Second Embodiment

Hereinafter, Second Embodiment of the present invention is explained.The same matters as First Embodiment are not explained.

In Second Embodiment, a soft magnetic alloy before heat treatment iscomposed of only amorphous phases. Even if the soft magnetic alloybefore heat treatment is composed of only amorphous phases, contains noinitial fine crystals, and has no nanohetero structure, a soft magneticalloy having a Fe based nanocrystalline structure, namely, a softmagnetic alloy according to the third aspect of the present inventioncan be obtained by heat treatment.

Compared to First Embodiment, however, Fe based nanocrystallines arehard to be deposited by heat treatment, and the average grain size ofthe Fe based nanocrystallines is hard to be controlled. Thus, excellentcharacteristics are hard to be obtained compared to First Embodiment.

Third Embodiment

Hereinafter, Third Embodiment of the present invention is explained. Thesame matters as First Embodiment are not explained.

The soft magnetic alloy according to the present embodiment includes amain component of(Fe_((1−(α+β)))X1_(α)X2_(β))_((1−(a+b+c+d+e)))M_(a)B_(b)P_(c)Si_(d)C_(e),in which

X1 is one or more of Co and Ni,

X2 is one or more of Al, Mn, Ag, Zn, Sn, As, Sb, Cu, Cr, Bi, N, O, andrare earth elements,

M is one or more of Nb, Hf, Zr, Ta, Mo, W, and V,

0.020≤a≤0.14 is satisfied,

0.020<b≤0.20 is satisfied,

0<c≤0.040 is satisfied,

0≤d≤0.060 is satisfied,

0.0005<e<0.0050 is satisfied,

α≥0 is satisfied,

β≥0 is satisfied, and

0≤α+β≤0.50 is satisfied,

wherein the soft magnetic alloy has a nanohetero structure where initialfine crystals exist in an amorphous phase.

When the above-mentioned soft magnetic alloy (a soft magnetic alloyaccording to the second aspect of the present invention) undergoes aheat treatment, Fe based nanocrystallines are easily deposited in thesoft magnetic alloy. In other words, the above-mentioned soft magneticalloy easily becomes a starting raw material of a soft magnetic alloywhere Fe based nanocrystallines are deposited (a soft magnetic alloyaccording to the fourth aspect of the present invention). Incidentally,the initial fine crystals preferably have an average grain size of 0.3to 10 nm.

The soft magnetic alloy according to the fourth aspect of the presentinvention has the same main component as the soft magnetic alloyaccording to the second aspect and has a structure of Fe basednanocrystallines.

The content P (c) satisfies 0<c≤0.040. The content P (c) is preferably0.010≤c≤0.040, more preferably 0.020≤c≤0.030. When the content P (c) isin the above range, the soft magnetic alloy has an improved resistivityand a low coercivity. Moreover, when the soft magnetic alloy has animproved resistivity, a high permeability μ′ can be maintained to ahigher frequency. When c=0 is satisfied, the above-mentioned effectscannot be obtained.

The C content (e) satisfies 0.0005≤e≤0.0050. The C content (e) ispreferably 0.0006≤e≤0.0045, more preferably 0.0020≤e≤0.0045. When the Ccontent (e) is larger than 0.0005, the soft magnetic alloy easily has animproved resistivity and particularly easily has a low coercivity, and ahigh permeability μ′ can be maintained to a high frequency. When the Ccontent (e) is too large, saturation magnetic flux density is decreased.

Preferably, X2 is one or more of Al, Mn, Ag, Zn, Sn, As, Sb, Cu, Cr, Bi,N, O, and rare earth elements. When X2 is one or more of Al, Mn, Ag, Zn,Sn, As, Sb, Cu, Cr, Bi, N, O, and rare earth elements, it becomes easierto obtain a soft magnetic alloy containing no crystal phases composed ofcrystals having a grain size of larger than 30 nm (a soft magnetic alloyaccording to the second aspect of the present invention). When this softmagnetic alloy undergoes a heat treatment, it becomes easier to obtain asoft magnetic alloy having a structure of Fe based nanocrystallines (asoft magnetic alloy according to the fourth aspect of the presentinvention).

Fourth Embodiment

Hereinafter, Fourth Embodiment of the present invention is explained.The same matters as Third Embodiment are not explained.

In Fourth Embodiment, a soft magnetic alloy before heat treatment iscomposed of only amorphous phases. Even if the soft magnetic alloybefore heat treatment is composed of only amorphous phases, contains noinitial fine crystals, and has no nanohetero structure, a soft magneticalloy having a Fe based nanocrystalline structure, namely, a softmagnetic alloy according to the fourth aspect of the present inventioncan be obtained by heat treatment.

Compared to Third Embodiment, however, Fe based nanocrystallines arehard to be deposited by heat treatment, and the average grain size ofthe Fe based nanocrystallines is hard to be obtained. Thus, excellentcharacteristics are hard to be obtained compared to Third Embodiment.

Fifth Embodiment

A magnetic device, especially a magnetic core and an inductor, accordingto Fifth Embodiment is obtained from the soft magnetic alloy accordingto any of First Embodiment to Fourth Embodiment. Hereinafter, a magneticcore and an inductor according to Fifth Embodiment are explained, butthe following method is not the only one method for obtaining themagnetic core and the inductor from the soft magnetic alloy. In additionto inductors, the magnetic core is used for transformers, motors, andthe like.

For example, a magnetic core from a ribbon-shaped soft magnetic alloy isobtained by winding or laminating the ribbon-shaped soft magnetic alloy.When the ribbon-shaped soft magnetic alloy is laminated via aninsulator, a magnetic core having further improved properties can beobtained.

For example, a magnetic core from a powder-shaped soft magnetic alloy isobtained by appropriately mixing the powder-shaped soft magnetic alloywith a binder and pressing this using a die. When an oxidationtreatment, an insulation coating, or the like is carried out against thesurface of the powder before the mixture with the binder, resistivity isimproved, and the magnetic core becomes more suitable for high-frequencyregions.

The pressing method is not limited. Examples of the pressing methodinclude a pressing using a die and a mold pressing. There is no limit tothe type of the binder. Examples of the binder include a silicone resin.There is no limit to a mixture ratio between the soft magnetic alloypowder and the binder either. For example, 1 to 10 mass % of the binderis mixed with 100 mass % of the soft magnetic alloy powder.

For example, 100 mass % of the soft magnetic alloy powder is mixed with1 to 5 mass % of a binder and compressively pressed using a die, and itis thereby possible to obtain a magnetic core having a space factor(powder filling rate) of 70% or more, a magnetic flux density of 0.45 Tor more at the time of applying a magnetic field of 1.6×10⁴ A/m, and aresistivity of 1 Ω·cm or more. These properties are equivalent to ormore excellent than those of normal ferrite magnetic cores.

For example, 100 mass % of the soft magnetic alloy powder is mixed with1 to 3 mass % of a binder and compressively pressed using a die under atemperature condition that is equal to or higher than a softening pointof the binder, and it is thereby possible to obtain a dust core having aspace factor of 80% or more, a magnetic flux density of 0.9 T or more atthe time of applying a magnetic field of 1.6×10⁴ A/m, and a resistivityof 0.1 Ω·cm or more. These properties are more excellent than those ofnormal dust cores.

Moreover, a green compact constituting the above-mentioned magnetic coreundergoes a heat treatment after the pressing for distortion removal.This further reduces core loss and improves usefulness. Incidentally,core loss of the magnetic core is decreased by reduction in coercivityof a magnetic material constituting the magnetic core.

An inductance product is obtained by winding a wire around theabove-mentioned magnetic core. The wire is wound by any method, and theinductance product is manufactured by any method. For example, a wire iswound around a magnetic core manufactured by the above-mentioned methodat least in one or more turns.

Moreover, when using soft magnetic alloy grains, there is a method ofmanufacturing an inductance product by pressing and integrating amagnetic material incorporating a wire coil. In this case, an inductanceproduct corresponding to high frequencies and large electric current isobtained easily.

Moreover, when using soft magnetic alloy grains, an inductance productcan be obtained by carrying out firing after alternately printing andlaminating a soft magnetic alloy paste obtained by pasting the softmagnetic alloy grains added with a binder and a solvent and a conductorpaste obtained by pasting a conductor metal for coils added with abinder and a solvent. Instead, an inductance product where a coil isincorporated into a magnetic material can be obtained by preparing asoft magnetic alloy sheet using a soft magnetic alloy paste, printing aconductor paste on the surface of the soft magnetic alloy sheet, andlaminating and firing them.

Here, when an inductance product is manufactured using soft magneticalloy grains, in view of obtaining excellent Q properties, it ispreferred to use a soft magnetic alloy powder whose maximum grain sizeis 45 m or less by sieve diameter and center grain size (D50) is 30 μmor less. In order to have a maximum grain size of 45 μm or less by sievediameter, only a soft magnetic alloy powder that passes through a sievewhose mesh size is 45 μm may be used.

The larger a maximum grain size of a soft magnetic alloy powder is, thefurther Q values in high-frequency regions tend to decrease. Inparticular, when using a soft magnetic alloy powder whose maximum graindiameter is larger than 45 μm by sieve diameter, Q values inhigh-frequency regions may decrease greatly. When Q values inhigh-frequency regions are not so important, however, a soft magneticalloy powder having a large variation can be used. When a soft magneticalloy powder having a large variation is used, cost can be reduced as itcan be manufactured comparatively inexpensively.

Hereinbefore, the embodiments of the present invention are explained,but the present invention is not limited to the above embodiments.

The soft magnetic alloy has any shape. For example, the soft magneticalloy has a ribbon shape or a powder shape as mentioned above, but mayhave another shape of block etc.

The soft magnetic alloys (Fe based nanocrystalline alloys) according toFirst Embodiment to Fourth Embodiment are used for any purposes, such asmagnetic devices (particularly magnetic cores), and can favorably beused as magnetic cores for inductors (particularly for power inductors).In addition to magnetic cores, the soft magnetic alloys according to theembodiments can favorably be used for thin film inductors and magneticheads.

EXAMPLES

Hereinafter, the present invention is specifically explained based onExamples.

Experimental Example 1

Raw material metals were weighed so that the alloy compositions ofExamples and Comparative Examples shown in the following table would beobtained, and the weighed raw material metals were melted byhigh-frequency heating. Then, base alloys were manufactured.Incidentally, the compositions of Sample No. 9 and Sample No. 10 were acomposition of a normally well-known amorphous alloy.

The manufactured base alloys were thereafter heated, melted, and turnedinto a molten metal at 1250° C. This metal was sprayed against a rollerrotating at 25 m/sec. (single roller method), and ribbons were therebyobtained. Incidentally, the roller was made of Cu.

In Sample No. 1 to Sample No. 4, the roller was rotated in the directionshown in FIG. 2, and the roller temperature was 30° C. In Sample No. 1to Sample No. 4, the roller rotating speed was controlled, and theribbons to be obtained thereby had a thickness of 20 μm to 30 μm, awidth of 4 mm to 5 mm, and a length of several tens of meter.

In Sample No. 5 to Sample No. 10, the roller was rotated in thedirection shown in FIG. 1, and the roller temperature was 70° C. InSample No. 5 to Sample No. 10, the ribbon to be obtained had a thicknessof 20 μm to 30 μm, a width of 4 mm to 5 mm, and a length of several tensof meter, provided that the differential pressure between the inside ofthe chamber and the inside of the spray nozzle was 105 kPa, that thenozzle diameter was 5 mm slit, that the flow rate was 50 g, and that theroller diameter φ was 300 mm.

In Sample No. 7a and Sample No. 8a, the roller was rotated in thedirection shown in FIG. 1, and the roller temperature was 30° C. InSample No. 7a and Sample No. 8a, the ribbon to be obtained had athickness of 20 μm to 30 μm, a width of 4 mm to 5 mm, and a length ofseveral tens of meter, provided that the differential pressure betweenthe inside of the chamber and the inside of the spray nozzle was 105kPa, that the nozzle diameter was 5 mm slit, that the flow rate was 50g, and that the roller diameter φ was 300 mm.

Each of the obtained ribbons underwent an X-ray diffraction measurementand was confirmed if it contained crystals having a grain size of largerthan 30 nm. When crystals having a grain size of larger than 30 nm didnot exist, the ribbon was considered to be composed of amorphous phases.When crystals having a grain size of larger than 30 nm existed, theribbon was considered to be composed of crystalline phases.Incidentally, all of Examples except for Sample No. 135 mentioned belowhad a nanohetero structure where initial fine crystals existed inamorphous phases.

After that, each ribbon of Examples and Comparative Examples underwent aheat treatment with the conditions shown in the following table. Eachribbon after the heat treatment was measured for resistivity, saturationmagnetic flux density, coercivity, and permeability μ′. The resistivity(φ was measured by four probe method. The saturation magnetic fluxdensity (Bs) was measured in a magnetic field of 1000 kA/m using avibrating sample type magnetometer (VSM). The coercivity (Hc) wasmeasured in a magnetic field of 5 kA/m using a DC BH tracer. Thepermeability μ′ was measured by changing frequency using an impedanceanalyzer and was evaluated as a frequency when the permeability μ′became 10000 (hereinafter, also referred to as a specific frequency f).In Experimental Examples 1 to 3, a resistivity of 110 μΩcm or more wasrepresented by ⊚, a resistivity of 100 gΩcm or more and less than 110μΩcm was represented by ∘, and a resistivity of less than 100 μΩcm wasx. The evaluation was higher in the order of ⊚, ∘, and x. The evaluationof ⊚ and ∘ was considered to be good. In Experimental Examples 1 to 3, asaturation magnetic flux density of 1.35 T or more was considered to begood, and a saturation magnetic flux density of 1.40 T or more wasconsidered to be better. In Experimental Examples 1 to 3, a coercivityof 3.0 A/m or less was considered to be good, a coercivity of 2.5 A/m orless was considered to be better, a coercivity of 2.0 A/m or less wasconsidered to be still better, and a coercivity of 1.5 A/m or less wasconsidered to be best. In Experimental Examples 1 to 3, the permeabilityμ′ was considered to be good when a specific frequency f was 100 kHz ormore.

Unless otherwise noted, a measurement of X-ray diffraction and anobservation using a transmission electron microscope confirmed that allof Examples shown below contained Fe based nanocrystallines having anaverage grain size of 5 to 30 nm and having a crystal structure of bcc.An ICP analysis also confirmed that the alloy composition did not changebefore and after the heat treatment.

TABLE 1 (Fe (1 − (a + b + c + d + e) ) MaBbPcSidCe (α = β = 0)saturation magnetic specific Com- roller roller resis- coer- flux fre-parative contact temp- tivity civity density quency Sample Example/distance erature M(Nb) B P Si C ρ Hc Bs f No. Example (cm) (° C.) Fe a bc d e XRD (μ Ω cm) (A/m) (T) (kHz)  1 Comp. 6 30 0.840 0.070 0.090 0.0000.000 0.000 amor- X 6.3 1.58 30 Ex. phous phase  2 Comp. 6 30 0.8200.070 0.090 0.020 0.000 0.000 amor- X 2.4 1.54 50 Ex. phous phase  3Comp. 6 30 0.795 0.070 0.090 0.045 0.000 0.000 crystal- X 189 1.43 — Ex.line phase  4 Comp. 6 30 0.760 0.070 0.090 0.080 0.000 0.000 crystal- X2740 1.41 — Ex. line phase  5 Comp. 18 70 0.840 0.070 0.090 0.000 0.0000.000 amor- X 6.1 1.58 40 Ex. phous phase  6 Comp. 18 70 0.820 0.0700.090 0.020 0.000 0.000 amor- X 2.3 1.53 60 Ex. phous phase  7 Ex. 18 700.795 0.070 0.090 0.045 0.000 0.000 amor- ◯ 2.0 1.49 110 phous phase  8Ex. 18 70 0.760 0.070 0.090 0.080 0.000 0.000 amor- ◯ 2.2 1.47 130 phousphase  7a Comp. 18 30 0.795 0.070 0.090 0.045 0.000 0.000 crystal- X 2871.41 — Ex. line phase  8a Comp. 18 30 0.760 0.070 0.090 0.080 0.0000.000 crystal- X 2931 1.42 — Ex. line phase  9 Comp. 18 70 0.780 0.0000.130 0.000 0.090 0.000 amor- ⊚ 1.5 1.60 40 Ex. phous phase 10 Comp. 1870 Co66Fe4Si17B13 amor- ⊚ 2.2 0.50 80 Ex. phous phase

Table 1 shows that all characteristics were good in Sample No. 7 andSample No. 8 (each component content was in a predetermined range, andthe roller contact distance and the roller temperature were controlledfavorably). On the other hand, Table 1 shows that any of characteristicswas bad in Sample No. 1, Sample No. 2, Sample No. 5, Sample No. 6,Sample No. 9, and Sample No. 10 (each component content, especially Pcontent, was outside a predetermined range). Table 1 also shows that theribbon before the heat treatment was composed of crystalline phases andhad a small resistivity, a significantly large coercivity, asignificantly small permeability μ′, and no specific frequency f afterthe heat treatment in Sample No. 3, Sample No. 4, Sample No. 7a, andSample No. 8a (each component content was in a predetermined range, butthe roller contact distance and/or the roller temperature was/were notcontrolled favorably).

Experimental Example 2

Experimental Example 2 was carried out with the same conditions asSample No. 5 to Sample No. 10 of Experimental Example 1 except that basealloys were manufactured by weighing raw material metals so that alloycompositions of Examples and Comparative Examples shown in the followingtables would be obtained and by melting the raw material metals withhigh-frequency heating.

TABLE 2 (Fe (1 − (a + b + c + d + e) ) MaBbPcSidCe (α = β = 0)saturation magnetic specific Com- resis- coer- flux fre- parative tivitycivity density quency Sample Example/ M(Nb) B P Si C ρ Hc Bs f No.Example Fe a b c d e XRD (μ Ω cm) (A/m) (T) (kHz) 12 Comp. 0.845 0.0150.090 0.050 0.000 0.000 crystal- X 336 1.46 — Ex. line phase 13 Ex.0.840 0.020 0.090 0.050 0.000 0.000 amor- ◯ 2.8 1.58 110 phous phase 14Ex. 0.820 0.040 0.090 0.050 0.000 0.000 amor- ◯ 2.4 1.56 120 phous phase15 Ex. 0.810 0.050 0.090 0.050 0.000 0.000 amor- ◯ 1.9 1.53 150 phousphase 11 Ex. 0.800 0.060 0.090 0.050 0.000 0.000 amor- ◯ 1.8 1.52 110phous phase 16 Ex. 0.780 0.080 0.090 0.050 0.000 0.000 amor- ◯ 1.8 1.48140 phous phase 17 Ex. 0.760 0.100 0.090 0.050 0.000 0.000 amor- ◯ 2.31.44 130 phous phase 18 Ex. 0.740 0.120 0.090 0.050 0.000 0.000 amor- ◯2.7 1.42 140 phous phase 19 Ex. 0.720 0.140 0.090 0.050 0.000 0.000amor- ◯ 2.7 1.38 150 phous phase 20 Comp. 0.710 0.150 0.090 0.050 0.0000.000 amor- ◯ 2.9 1.22 150 Ex. phous phase 21 Comp. 0.870 0.060 0.0200.050 0.000 0.000 crystal- X 217 1.60 — Ex. line phase 22 Ex. 0.8650.060 0.025 0.050 0.000 0.000 amor- ◯ 2.6 1.62 110 phous phase 23 Ex.0.830 0.060 0.060 0.050 0.000 0.000 amor- ◯ 2.1 1.57 110 phous phase 24Ex. 0.810 0.060 0.080 0.050 0.000 0.000 amor- ◯ 1.8 1.56 120 phous phase11 Ex. 0.800 0.060 0.090 0.050 0.000 0.000 amor- ◯ 1.8 1.52 110 phousphase 25 Ex. 0.770 0.060 0.120 0.050 0.000 0.000 amor- ◯ 2.0 1.45 130phous phase 26 Ex. 0.740 0.060 0.150 0.050 0.000 0.000 amor- ◯ 2.5 1.40130 phous phase 27 Ex. 0.690 0.060 0.200 0.050 0.000 0.000 amor- ◯ 2.71.35 130 phous phase 28 Comp. 0.680 0.060 0.210 0.050 0.000 0.000 amor-◯ 2.9 1.20 140 Ex. phous phase 29 Comp. 0.810 0.060 0.090 0.040 0.0000.000 amor- X 3.3 1.49 90 Ex. phous phase 30 Ex. 0.809 0.060 0.090 0.0410.000 0.000 amor- ◯ 2.6 1.47 100 phous phase 31 Ex. 0.805 0.060 0.0900.045 0.000 0.000 amor- ◯ 2.3 1.46 110 phous phase 11 Ex. 0.800 0.0600.090 0.050 0.000 0.000 amor- ◯ 1.8 1.52 110 phous phase 32 Ex. 0.7800.060 0.090 0.070 0.000 0.000 amor- ◯ 1.8 1.40 120 phous phase 33 Ex.0.770 0.060 0.090 0.080 0.000 0.000 amor- ◯ 2.2 1.43 130 phous phase 34Ex. 0.750 0.060 0.090 0.100 0.000 0.000 amor- ◯ 2.5 1.41 140 phous phase35 Ex. 0.700 0.060 0.090 0.150 0.000 0.000 amor- ◯ 2.7 1.37 140 phousphase 36 Comp. 0.690 0.060 0.090 0.160 0.000 0.000 amor- ◯ 2.8 1.28 140Ex. phous phase 11 Ex. 0.800 0.060 0.090 0.050 0.000 0.000 amor- ◯ 1.81.52 110 phous phase 37 Ex. 0.799 0.060 0.090 0.050 0.000 0.001 amor- ◯1.4 1.51 140 phous phase 38 Ex. 0.795 0.060 0.090 0.050 0.000 0.005amor- ◯ 1.2 1.51 150 phous phase 39 Ex. 0.790 0.060 0.090 0.050 0.0000.010 amor- ◯ 1.5 1.50 140 phous phase 40 Ex. 0.770 0.060 0.090 0.0500.000 0.030 amor- ◯ 1.7 1.48 120 phous phase 41 Comp. 0.760 0.060 0.0900.050 0.000 0.040 amor- X 3.2 1.43 80 Ex. phous phase 42 Ex. 0.795 0.0600.090 0.050 0.005 0.000 amor- ◯ 1.7 1.53 140 phous phase 43 Ex. 0.7900.060 0.090 0.050 0.010 0.000 amor- ⊚ 1.6 1.52 200 phous phase 44 Ex.0.780 0.060 0.090 0.050 0.020 0.000 amor- ⊚ 1.6 1.50 230 phous phase 45Ex. 0.770 0.060 0.090 0.050 0.030 0.000 amor- ⊚ 2.1 1.46 240 phous phase46 Ex. 0.740 0.060 0.090 0.050 0.060 0.000 amor- ⊚ 2.5 1.42 250 phousphase 47 Comp. 0.730 0.060 0.090 0.050 0.070 0.000 amor- ⊚ 3.8 1.40 180Ex. phous phase 48 Ex. 0.794 0.060 0.090 0.045 0.010 0.001 amor- ⊚ 1.31.54 210 phous phase 49 Ex. 0.780 0.060 0.090 0.045 0.020 0.005 amor- ⊚1.5 1.49 200 phous phase 50 Ex. 0.730 0.080 0.120 0.070 0.000 0.000amor- ◯ 2.9 1.40 130 phous phase 11 Ex. 0.800 0.060 0.090 0.050 0.0000.000 amor- ◯ 1.8 1.52 110 phous phase 51 Ex. 0.880 0.040 0.030 0.0500.000 0.000 amor- ◯ 2.7 1.67 140 phous phase 52 Ex. 0.900 0.030 0.0290.041 0.000 0.000 amor- ◯ 2.6 1.7 150 phous phase

TABLE 3 Fe (1 − (a + b + c + d + e) ) MaBbPcSidCe (α = β = 0, b to e arethe same as those of Sample No. 14, Sample No. 11, or Sample No. 18)saturation magnetic flux specific Comparative resistivity coercivitydensity frequency Sample Example/ M ρ Hc Bs f No. Example type a XRD (μΩ cm) (A/m) (T) (kHz) 14 Ex. Nb 0.040 amorphous ◯ 2.4 1.56 120 phase 53Ex. Hf 0.040 amorphous ◯ 2.5 1.54 130 phase 54 Ex. Zr 0.040 amorphous ◯2.3 1.55 120 phase 55 Ex. Ta 0.040 amorphous ◯ 2.3 1.53 110 phase 56 Ex.Mo 0.040 amorphous ◯ 2.5 1.56 120 phase 57 Ex. W 0.040 amorphous ◯ 2.51.53 130 phase 58 Ex. V 0.040 amorphous ◯ 2.4 1.53 120 phase 59 Ex.Nb0.5Hf0.5 0.040 amorphous ◯ 2.4 1.55 110 phase 60 Ex. Zr0.5Ta0.5 0.040amorphous ◯ 2.3 1.53 120 phase 61 Ex. Nb0.4Hf0.3Zr0.3 0.040 amorphous ◯2.4 1.54 120 phase 11 Ex. Nb 0.060 amorphous ◯ 1.8 1.52 110 phase 62 Ex.Hf 0.060 amorphous ◯ 1.8 1.51 120 phase 63 Ex. Zr 0.060 amorphous ◯ 1.71.52 120 phase 64 Ex. Ta 0.060 amorphous ◯ 1.7 1.53 130 phase 65 Ex. Mo0.060 amorphous ◯ 2.0 1.50 110 phase 66 Ex. W 0.060 amorphous ◯ 2.0 1.50110 phase 67 Ex. V 0.060 amorphous ◯ 1.9 1.51 110 phase 68 Ex.Nb0.5Hf0.5 0.060 amorphous ◯ 1.8 1.52 120 phase 69 Ex. Zr0.5Ta0.5 0.060amorphous ◯ 1.9 1.53 130 phase 70 Ex. Nb0.4Hf0.3Zr0.3 0.060 amorphous ◯2.0 1.51 130 phase 18 Ex. Nb 0.120 amorphous ◯ 2.7 1.42 140 phase 71 Ex.Hf 0.120 amorphous ◯ 2.6 1.41 140 phase 72 Ex. Zr 0.120 amorphous ◯ 2.71.43 120 phase 73 Ex. Ta 0.120 amorphous ◯ 2.8 1.43 130 phase 74 Ex. Mo0.120 amorphous ◯ 2.5 1.40 120 phase 75 Ex. W 0.120 amorphous ◯ 2.6 1.40120 phase 76 Ex. V 0.120 amorphous ◯ 2.8 1.41 100 phase 77 Ex.Nb0.5Hf0.5 0.120 amorphous ◯ 2.6 1.42 110 phase 78 Ex. Zr0.5Ta0.5 0.120amorphous ◯ 2.8 1.41 120 phase 79 Ex. Nb0.4Hf0.3Zr0.3 0.120 amorphous ◯2.8 1.42 130 phase

TABLE 4 Fe (1 − (α + β)) X1αX2β (a to e are the same as those of SampleNo. 11) saturation magnetic flux specific Comparative X1 X2 resistivitycoercivity density frequency Sample Example/ α|1 − β|1 − ρ Hc Bs f No.Example type (a + b + c + d + e)| type (a + b + c + d + e)| XRD (μ Ω cm)(A/m) (T) (kHz) 11 Ex. — 0.000 — 0.000 amorphous ◯ 1.8 1.52 110 phase 81Ex. Co 0.010 — 0.000 amorphous ◯ 2.1 1.53 120 phase 82 Ex. Co 0.100 —0.000 amorphous ◯ 2.5 1.55 120 phase 83 Ex. Co 0.400 — 0.000 amorphous ◯2.9 1.60 120 phase 84 Ex. Ni 0.010 — 0.000 amorphous ◯ 1.8 1.51 120phase 85 Ex. Ni 0.100 — 0.000 amorphous ◯ 1.7 1.47 120 phase 86 Ex. Ni0.400 — 0.000 amorphous ◯ 1.6 1.42 130 phase 87 Ex. — 0.000 Al 0.001amorphous ◯ 1.8 1.52 110 phase 88 Ex. — 0.000 Al 0.005 amorphous ⊚ 1.81.51 110 phase 89 Ex. — 0.000 Al 0.010 amorphous ⊚ 1.7 1.51 110 phase 90Ex. — 0.000 Al 0.030 amorphous ⊚ 1.8 1.50 120 phase 91 Ex. — 0.000 Zn0.001 amorphous ◯ 1.8 1.50 110 phase 92 Ex. — 0.000 Zn 0.005 amorphous ◯1.9 1.52 120 phase 93 Ex. — 0.000 Zn 0.010 amorphous ⊚ 1.8 1.50 120phase 94 Ex. — 0.000 Zn 0.030 amorphous ⊚ 1.9 1.51 130 phase 95 Ex. —0.000 Sn 0.001 amorphous ◯ 1.8 1.52 110 phase 96 Ex. — 0.000 Sn 0.005amorphous ⊚ 1.9 1.51 110 phase 97 Ex. — 0.000 Sn 0.010 amorphous ⊚ 1.91.52 110 phase 98 Ex. — 0.000 Sn 0.030 amorphous ⊚ 2.0 1.50 110 phase 99Ex. — 0.000 Cu 0.001 amorphous ⊚ 1.6 1.52 110 phase 100 Ex. — 0.000 Cu0.005 amorphous ⊚ 1.7 1.52 110 phase 101 Ex. — 0.000 Cu 0.010 amorphous⊚ 1.5 1.52 120 phase 102 Ex. — 0.000 Cu 0.030 amorphous ⊚ 1.6 1.54 130phase 103 Ex. — 0.000 Cr 0.001 amorphous ⊚ 1.8 1.52 110 phase 104 Ex. —0.000 Cr 0.005 amorphous ⊚ 1.7 1.51 110 phase 105 Ex. — 0.000 Cr 0.010amorphous ⊚ 1.8 1.50 120 phase 106 Ex. — 0.000 Cr 0.030 amorphous ⊚ 1.91.51 120 phase 107 Ex. — 0.000 Bi 0.001 amorphous ⊚ 1.8 1.51 120 phase108 Ex. — 0.000 Bi 0.005 amorphous ⊚ 1.7 1.50 120 phase 109 Ex. — 0.000Bi 0.010 amorphous ⊚ 1.8 1.49 120 phase 110 Ex. — 0.000 Bi 0.030amorphous ⊚ 2.0 1.48 120 phase 111 Ex. — 0.000 La 0.001 amorphous ⊚ 1.81.52 110 phase 112 Ex. — 0.000 La 0.005 amorphous ⊚ 1.9 1.51 110 phase113 Ex. — 0.000 La 0.010 amorphous ⊚ 2.1 1.49 110 phase 114 Ex. — 0.000La 0.030 amorphous ⊚ 2.1 1.48 110 phase 115 Ex. — 0.000 Y 0.001amorphous ⊚ 1.9 1.51 110 phase 116 Ex. — 0.000 Y 0.005 amorphous ⊚ 1.81.49 120 phase 117 Ex. — 0.000 Y 0.010 amorphous ⊚ 1.8 1.48 120 phase118 Ex. — 0.000 Y 0.030 amorphous ⊚ 2.0 1.49 120 phase 119 Ex. Co 0.100Al 0.050 amorphous ⊚ 2.1 1.52 120 phase 120 Ex. Co 0.100 Zn 0.050amorphous ⊚ 2.2 1.54 120 phase 121 Ex. Co 0.100 Sn 0.050 amorphous ⊚ 2.21.53 120 phase 122 Ex. Co 0.100 Cu 0.050 amorphous ⊚ 2.0 1.53 120 phase123 Ex. Co 0.100 Cr 0.050 amorphous ⊚ 2.1 1.53 120 phase 124 Ex. Co0.100 Bi 0.050 amorphous ⊚ 2.2 1.51 130 phase 125 Ex. Co 0.100 La 0.050amorphous ⊚ 2.3 1.52 110 phase 126 Ex. Co 0.100 Y 0.050 amorphous ⊚ 2.31.53 120 phase 127 Ex. Ni 0.100 Al 0.050 amorphous ⊚ 1.7 1.48 130 phase128 Ex. Ni 0.100 Zn 0.050 amorphous ⊚ 1.7 1.47 130 phase 129 Ex. Ni0.100 Sn 0.050 amorphous ⊚ 1.6 1.48 120 phase 130 Ex. Ni 0.100 Cu 0.050amorphous ⊚ 1.6 1.49 140 phase 131 Ex. Ni 0.100 Cr 0.050 amorphous ⊚ 1.71.47 130 phase 132 Ex. Ni 0.100 Bi 0.050 amorphous ⊚ 1.8 1.48 120 phase133 Ex. Ni 0.100 La 0.050 amorphous ⊚ 1.8 1.46 130 phase 134 Ex. Ni0.100 Y 0.050 amorphous ⊚ 1.8 1.45 120 phase

Table 2 shows examples whose M content (a), B content (b), P content(c), Si content (d), and C content (e) were changed. Incidentally, thetype of M was Nb. Examples whose each component content was in apredetermined range had a good resistivity ρ, a good saturation magneticflux density Bs, a good coercivity Hc, and a good permeability μ′.

In Sample No. 12 (M content (a) was too small), the ribbon before theheat treatment was composed of crystalline phases and had a smallresistivity ρ, a significantly large coercivity Hc, a significantlysmall permeability μ′, and no specific frequency f after the heattreatment. Sample No. 20 (M content (a) was too large) had a lowsaturation magnetic flux density Bs.

In Sample No. 21 (B content (a) was too small), the ribbon before theheat treatment was composed of crystalline phases and had a smallresistivity ρ, a significantly large coercivity Hc, a significantlysmall permeability μ′, and no specific frequency f after the heattreatment. Sample No. 28 (B content (a) was too large) had a lowsaturation magnetic flux density Bs.

Sample No. 29 (P content (c) was too small) had a small resistivity ρ, alarge coercivity Hc, a small permeability μ′, and a small specificfrequency f after the heat treatment. Sample No. 36 (P content (c) wastoo large) had a low saturation magnetic flux density Bs.

Sample No. 47 (Si content (d) was too large) had a large coercivity Hcafter the heat treatment. Sample No. 41 (C content (e) was too large)had a small resistivity ρ, a large coercivity Hc, a small permeabilityμ′, and a small specific frequency f after the heat treatment.

Table 3 shows Examples whose M type was changed in Sample No. 11, SampleNo. 14, and Sample No. 18. Sample No. 53 to 61 were Examples whose Mtype was changed in Sample No. 14. Sample No. 62 to 70 were Exampleswhose M type was changed in Sample No. 11. Sample No. 71 to 79 wereExamples whose M type was changed in Sample No. 18.

Table 3 shows that excellent characteristics were exhibited even if thetype of M was changed.

Table 4 shows Examples where a part of Fe was substituted by X1 and/orX2 in Sample No. 11.

Table 4 shows that excellent characteristics were exhibited even if apart of Fe was substituted by X1 and/or X2.

Experimental Example 3

In Experimental Example 3, the average grain size of the initial finecrystals and the average grain size of the Fe based nanocrystallinealloy in Sample No. 11 were changed by appropriately changing thetemperature of molten metal and the heat-treatment conditions after theribbon was manufactured. Table 5 shows the results. Incidentally, allsamples shown in Table 5 had a good permeability μ′.

TABLE 5 Fe (1 − (a + b + c + d + e) ) MaBbPcSidCe (α = β = 0, a to e arethe same as those of Sample No. 11) average average grain size grainsize heat heat of Fe based Comparative metal of initial fine treatmenttreatment nanocrystalline Sample Example/ temperature crystalstemperature time alloy ρ Hc Bs No. Example (° C.) (nm) (° C.) (h.) (nm)XRD (μ Ω cm) (A/m) (T) 135 Ex. 1200 no initial fine 800 1 10 amorphous ◯2.0 1.45 crystals phase 136 Ex. 1225 0.1 450 1 3 amorphous ◯ 2.0 1.48phase 137 Ex. 1250 0.3 500 1 5 amorphous ◯ 1.9 1.50 phase 138 Ex. 12500.3 550 1 10 amorphous ◯ 1.8 1.50 phase 139 Ex. 1250 0.3 575 1 13amorphous ◯ 1.7 1.51 phase 11 Ex. 1250 0.3 600 1 10 amorphous ◯ 1.8 1.52phase 141 Ex. 1275 10 600 1 12 amorphous ◯ 1.9 1.52 phase 142 Ex. 127510 650 1 30 amorphous ◯ 1.9 1.52 phase 143 Ex. 1300 15 600 1 17amorphous ◯ 2.3 1.51 phase 144 Ex. 1300 15 650 10 50 amorphous ◯ 2.91.43 phase

Table 5 shows that when the initial fine crystals had an average grainsize of 0.3 to 10 nm and when the Fe based nanocrystalline alloy had anaverage grain size of 5 to 30 nm, both saturation magnetic flux densityBs and coercivity Hc were good compared to those when these ranges werenot satisfied.

Experimental Example 4

Raw material metals were weighed so that the alloy compositions ofExamples and Comparative Examples shown in the following table wereobtained, and the weighed raw material metals were melted byhigh-frequency heating. Then, base alloys were manufactured.Incidentally, Sample No. 9 and Sample No. 10 were the same as Sample No.9 and Sample No. 10 in Experimental Example 1.

The manufactured base alloys were thereafter heated, melted, and turnedinto a molten metal at 1250° C. This molten metal was sprayed against aroller rotating at 25 m/sec. (single roller method), and ribbons werethereby obtained. Incidentally, the roller was made of Cu.

In Sample No. 201 and Sample No. 202, the roller was rotated in thedirection shown in FIG. 2, and the roller temperature was 30° C. InSample No. 201 and Sample No. 202, the roller rotating speed wascontrolled, and the ribbon to be obtained thereby had a thickness of 20nm to 30 μm, a width of 4 mm to 5 mm, and a length of several tens ofmeter.

In Sample No. 203 to Sample No. 209, the roller was rotated in thedirection shown in FIG. 1, and the roller temperature was 70° C. InSample No. 203 to Sample No. 209, the ribbon to be obtained had athickness of about 20 μm to 30 μm, a width of 4 mm to 5 mm, and a lengthof several tens of meter, provided that the differential pressurebetween the inside of the chamber and the inside of the spray nozzle was105 kPa, that the nozzle diameter was 5 mm slit, that the flow rate was50 g, and that the roller diameter φ was 300 mm.

Each of the obtained ribbons underwent an X-ray diffraction measurementand was confirmed if it contained crystals having a grain size of largerthan 30 nm. When crystals having a grain size of larger than 30 nm didnot exist, the ribbon was considered to be composed of amorphous phases.When crystals having a grain size of larger than 30 nm existed, theribbon was considered to be composed of crystalline phases.Incidentally, all of Examples except for Sample No. 274 mentioned belowhad a nanohetero structure where initial fine crystals existed inamorphous phases.

After that, the ribbons of Examples and Comparative Examples underwent aheat treatment with the conditions shown in the following table. Each ofthe ribbons after the heat treatment was measured for resistivity,saturation magnetic flux density, coercivity, and permeability μ′. Theresistivity (ρ) was measured by four probe method. The saturationmagnetic flux density (Bs) was measured in a magnetic field of 1000 kA/musing a vibrating sample type magnetometer (VSM). The coercivity (Hc)was measured in a magnetic field of 5 kA/m using a DC BH tracer. Thepermeability μ′ was measured by changing frequency using an impedanceanalyzer and was evaluated as a frequency when the permeability μ′became 10000 (hereinafter, also referred to as a specific frequency f).In Experimental Examples 4 to 6, a resistivity of 100 μΩcm or more wasrepresented by ⊚, a resistivity of 80 μΩcm or more and less than 100ρΩcm was represented by ∘, and a resistivity of less than 80 μΩcm was x.The evaluation was higher in the order of ⊚, ∘, and x. The evaluation of⊚ and ∘ was considered to be good. In Experimental Examples 4 to 6, asaturation magnetic flux density of 1.50 T or more was considered to begood. In Experimental Examples 4 to 6, a coercivity of 4.0 A/m or lesswas considered to be good. In Experimental Examples 4 to 6, thepermeability μ′ was considered to be good when a specific frequency fwas 70 kHz or more.

Unless otherwise noted, a measurement of X-ray diffraction and anobservation using a transmission electron microscope confirmed that allof Examples shown below contained Fe based nanocrystallines having anaverage grain size of 5 to 30 nm and having bcc crystal structure. AnICP analysis also confirmed that the alloy composition did not changebefore and after the heat treatment.

TABLE 6 (Fe (1 − (a + b + c + d + e) ) MaBbPcSidCe (α = β = 0)saturation magnetic specific Com- roller roller resis- coer- flux fre-parative contact temp- tivity civity density quency Sample Example/distance erature M(Nb) B P Si C ρ Hc Bs f No. Example (cm) (° C.) Fe a bc d e XRD (μ Ω cm) (A/m) (T) (kHz) 201 Comp. 6 30 0.840 0.070 0.0900.000 0.000 0.000 amor- X 6.3 1.58 30 Ex. phous phase 202 Comp. 6 300.820 0.070 0.090 0.020 0.000 0.000 amor- X 2.4 1.54 50 Ex. phous phase203 Comp. 18 70 0.840 0.070 0.090 0.000 0.000 0.000 amor- X 6.1 1.58 40Ex. phous phase 204 Comp. 18 70 0.820 0.070 0.090 0.020 0.000 0.000amor- X 2.3 1.53 60 Ex. phous phase 205 Comp. 18 70 0.838 0.070 0.0900.000 0.000 0.020 amor- X 3.1 1.53 50 Ex. phous phase 206 Ex. 18 700.818 0.070 0.090 0.020 0.000 0.020 amor- ◯ 1.8 1.56 80 phous phase 207Comp. 18 70 0.835 0.070 0.090 0.000 0.000 0.050 amor- X 2.6 1.46 60 Ex.phous phase 208 Comp. 18 70 0.815 0.070 0.090 0.020 0.000 0.050 amor- ◯2.7 1.45 60 Ex. phous phase 209 Comp. 18 30 0.838 0.070 0.090 0.0000.000 0.020 amor- X 3.3 1.53 50 Ex. phous phase 9 Comp. 18 70 0.7800.000 0.130 0.000 0.090 0.000 amor- ⊚ 1.5 1.60 40 Ex. phous phase 10Comp. 18 70 Co66Fe4Si17B13 amor- ⊚ 2.2 0.50 80 Ex. phous phase

Table 6 shows that all characteristics were good in Sample No. 206 (eachcomponent content was in a predetermined range, and the roller contactdistance and the roller temperature were controlled favorably). On theother hand, Table 6 shows that any of characteristics was bad in SampleNo. 201 to Sample No. 205 and Sample No. 207 to Sample No. 209 (eachcomponent content, especially P content and/or C content, was outside apredetermined range).

Experimental Example 5

Experimental Example 5 was carried out with the same conditions asSample No. 206 of Experimental Example 4 except that base alloys weremanufactured by weighing raw material metals so that alloy compositionsof Examples and Comparative Examples shown in the following tables wouldbe obtained and by melting the raw material metals with high-frequencyheating.

TABLE 7 (Fe (1 − (a + b + c + d + e) ) MaBbPcSidCe (α = β = 0)saturation magnetic specific Com- resis- coer- flux fre- parative tivitycivity density quency Sample Example/ M(Nb) B P Si C ρ Hc Bs f No.Example Fe a b c d e XRD (μ Ω cm) (A/m) (T) (kHz) 211 Comp. 0.873 0.0150.090 0.020 0.000 0.0020 crystal- X 458 1.68 — Ex. line phase 212 Ex.0.868 0.020 0.090 0.020 0.000 0.0020 amor- ◯ 3.2 1.66 70 phous phase 213Ex. 0.848 0.040 0.090 0.020 0.000 0.0020 amor- ◯ 2.9 1.64 70 phous phase214 Ex. 0.838 0.050 0.090 0.020 0.000 0.0020 amor- ◯ 2.3 1.62 80 phousphase 215 Ex. 0.828 0.060 0.090 0.020 0.000 0.0020 amor- ◯ 2.2 1.6 80phous phase 206 Ex. 0.818 0.070 0.090 0.020 0.000 0.0020 amor- ◯ 1.81.56 80 phous phase 216 Ex. 0.808 0.080 0.090 0.020 0.000 0.0020 amor- ◯1.8 1.55 80 phous phase 217 Ex. 0.788 0.100 0.090 0.020 0.000 0.0020amor- ◯ 1.9 1.53 80 phous phase 218 Ex. 0.768 0.120 0.090 0.020 0.0000.0020 amor- ◯ 2.1 1.52 90 phous phase 219 Ex. 0.748 0.140 0.090 0.0200.000 0.0020 amor- ◯ 2.4 1.5 90 phous phase 220 Comp. 0.738 0.150 0.0900.020 0.000 0.0020 amor- ◯ 2.6 1.43 80 Ex. phous phase 221 Comp. 0.8880.070 0.020 0.020 0.000 0.0020 crystal- X 678 1.77 — Ex. line phase 222Ex. 0.883 0.070 0.025 0.020 0.000 0.0020 amor- ◯ 3.8 1.71 80 phous phase223 Ex. 0.848 0.070 0.060 0.020 0.000 0.0020 amor- ◯ 3.3 1.62 80 phousphase 224 Ex. 0.828 0.070 0.080 0.020 0.000 0.0020 amor- ◯ 2.4 1.6 80phous phase 206 Ex. 0.818 0.070 0.090 0.020 0.000 0.0020 amor- ◯ 1.81.56 80 phous phase 225 Ex. 0.788 0.070 0.120 0.020 0.000 0.0020 amor- ◯1.6 1.55 80 phous phase 226 Ex. 0.758 0.070 0.150 0.020 0.000 0.0020amor- ◯ 1.8 1.53 90 phous phase 227 Ex. 0.708 0.070 0.200 0.020 0.0000.0020 amor- ◯ 2.1 1.5 90 phous phase 228 Comp. 0.698 0.070 0.210 0.0200.000 0.0020 amor- ◯ 2.2 1.48 80 Ex. phous phase 5 Comp. 0.840 0.0700.090 0.000 0.000 0.0000 amor- X 6.1 1.58 40 Ex. phous phase 205 Comp.0.838 0.070 0.090 0.000 0.000 0.0020 amor- X 4.8 1.58 50 Ex. phous phase229 Ex. 0.828 0.070 0.090 0.010 0.000 0.0020 amor- ◯ 3.1 1.52 80 phousphase 206 Ex. 0.818 0.070 0.090 0.020 0.000 0.0020 amor- ◯ 1.8 1.56 80phous phase 230 Ex. 0.808 0.070 0.090 0.030 0.000 0.0020 amor- ◯ 2.51.52 80 phous phase 231 Ex. 0.798 0.070 0.090 0.040 0.000 0.0020 amor- ◯3.1 1.52 80 phous phase 5 Comp. 0.840 0.070 0.090 0.000 0.000 0.0000amor- X 6.1 1.58 40 Ex. phous phase 232 Comp. 0.830 0.070 0.090 0.0100.000 0.0000 amor- X 4.2 1.55 60 Ex. phous phase 233 Ex. 0.829 0.0700.090 0.010 0.000 0.0006 amor- ◯ 3.8 1.54 80 phous phase 234 Ex. 0.8280.070 0.090 0.010 0.000 0.0020 amor- ◯ 3.1 1.52 80 phous phase 235 Ex.0.826 0.070 0.090 0.010 0.000 0.0045 amor- ◯ 2.8 1.51 80 phous phase 236Comp. 0.825 0.070 0.090 0.010 0.000 0.0050 amor- ◯ 2.5 1.45 60 Ex. phousphase 5 Comp. 0.840 0.070 0.090 0.000 0.000 0.0000 amor- X 6.1 1.58 40Ex. phous phase 6 Comp. 0.820 0.070 0.090 0.020 0.000 0.0000 amor- X 2.31.53 60 Ex. phous phase 237 Ex. 0.819 0.070 0.090 0.020 0.000 0.0006amor- ◯ 2.1 1.53 80 phous phase 206 Ex. 0.818 0.070 0.090 0.020 0.0000.0020 amor- ◯ 1.8 1.56 80 phous phase 238 Ex. 0.816 0.070 0.090 0.0200.000 0.0045 amor- ◯ 1.7 1.56 90 phous phase 208 Comp. 0.815 0.070 0.0900.020 0.000 0.0050 amor- ◯ 2.7 1.45 60 Ex. phous phase 5 Comp. 0.8400.070 0.090 0.000 0.000 0.0000 amor- X 6.1 1.58 40 Ex. phous phase 239Comp. 0.810 0.070 0.090 0.030 0.000 0.0000 amor- X 2.7 1.53 60 Ex. phousphase 240 Ex. 0.809 0.070 0.090 0.030 0.000 0.0006 amor- ◯ 2.6 1.54 70phous phase 241 Ex. 0.808 0.070 0.090 0.030 0.000 0.0020 amor- ◯ 2.51.52 80 phous phase 242 Ex. 0.806 0.070 0.090 0.030 0.000 0.0045 amor- ◯2.3 1.51 80 phous phase 243 Comp. 0.805 0.070 0.090 0.030 0.000 0.0050amor- ◯ 2.5 1.45 70 Ex. phous phase 5 Comp. 0.840 0.070 0.090 0.0000.000 0.0000 amor- X 6.1 1.58 40 Ex. phous phase 244 Comp. 0.800 0.0700.090 0.040 0.000 0.0000 amor- X 3.3 1.55 90 Ex. phous phase 245 Ex.0.799 0.070 0.090 0.040 0.000 0.0006 amor- ◯ 3.8 1.53 70 phous phase 246Ex. 0.798 0.070 0.090 0.040 0.000 0.0020 amor- ◯ 3.1 1.52 80 phous phase247 Ex. 0.796 0.070 0.090 0.040 0.000 0.0045 amor- ◯ 2.8 1.51 80 phousphase 248 Comp. 0.795 0.070 0.090 0.040 0.000 0.0050 amor- ◯ 2.5 1.42 70Ex. phous phase 206 Ex. 0.818 0.070 0.090 0.020 0.000 0.0020 amor- ◯ 1.81.56 80 phous phase 249 Ex. 0.798 0.070 0.090 0.020 0.020 0.0020 amor- ⊚2.4 1.54 80 phous phase 250 Ex. 0.778 0.070 0.090 0.020 0.040 0.0020amor- ⊚ 2.5 1.56 90 phous phase 251 Ex. 0.758 0.070 0.090 0.020 0.0600.0020 amor- ⊚ 2.4 1.51 90 phous phase 252 Comp. 0.738 0.070 0.090 0.0200.080 0.0020 amor- ◯ 2.7 1.42 70 Ex. phous phase

TABLE 8 Fe (1 − (a + b + c + d + e) ) MaBbPcSidCe (α = β = 0, b to e arethe same as those of Sample No. 206) saturation magnetic flux specificComparative resistivity coercivity density frequency Sample Example/ M ρHc Bs f No. Example type a XRD (μ Ω cm) (A/m) (T) (kHz) 206 Ex. Nb 0.070amorphous ◯ 1.8 1.56 80 phase 253 Ex. Hf 0.070 amorphous ◯ 1.8 1.55 80phase 254 Ex. Zr 0.070 amorphous ◯ 1.9 1.52 80 phase 255 Ex. Ta 0.070amorphous ◯ 2.4 1.51 70 phase 256 Ex. Mo 0.070 amorphous ◯ 2.4 1.51 80phase 257 Ex. W 0.070 amorphous ◯ 2.3 1.51 90 phase 258 Ex. V 0.070amorphous ◯ 2.4 1.52 80 phase 259 Ex. Nb0.5Hf0.5 0.070 amorphous ◯ 2.11.52 90 phase 260 Ex. Zr0.5Ta0.5 0.070 amorphous ◯ 2.3 1.53 90 phase 261Ex. Nb0.4Hf0.3Zr0.3 0.070 amorphous ◯ 2.1 1.51 90 phase

TABLE 9 Fe (1 − (α + β)) X1αX2β (a to e are the same as those of SampleNo. 206) saturation magnetic flux specific Comparative X1 X2 ribbonresistivity coercivity density frequency Sample Example/ α|1 − β|1 −thickness ρ Hc Bs f No. Example type (a + b + c + d + e)| type (a + b +c + d + e)| (μm) XRD (μ Ω cm) (A/m) (T) (kHz) 206 Ex. — 0.000 — 0.000 21amorphous ◯ 1.8 1.56 80 phase 262 Ex. Co 0.100 — 0.000 20 amorphous ◯2.4 1.56 80 phase 263 Ex. Co 0.400 — 0.000 22 amorphous ◯ 2.8 1.58 80phase 264 Ex. Ni 0.100 — 0.000 23 amorphous ◯ 2.1 1.54 80 phase 265 Ex.Ni 0.400 — 0.000 23 amorphous ◯ 2.4 1.53 80 phase 266 Ex. — 0.000 Al0.010 21 amorphous ⊚ 2.1 1.53 90 phase 267 Ex. — 0.000 Zn 0.010 20amorphous ⊚ 2.3 1.53 90 phase 268 Ex. — 0.000 Sn 0.010 21 amorphous ⊚2.3 1.54 80 phase 269 Ex. — 0.000 Cu 0.010 22 amorphous ⊚ 2.3 1.53 90phase 271 Ex. — 0.000 Bi 0.010 21 amorphous ⊚ 2.6 1.51 90 phase 272 Ex.— 0.000 La 0.010 20 amorphous ⊚ 2.7 1.52 80 phase 273 Ex. — 0.000 Y0.010 23 amorphous ⊚ 2.6 1.51 70 phase 273-2 Ex. — 0.000 Mn 0.010 22amorphous ⊚ 2.4 1.52 90 phase 273-3 Ex. — 0.000 Ag 0.010 21 amorphous ⊚2.3 1.51 90 phase 273-4 Ex. — 0.000 As 0.010 21 amorphous ⊚ 2.4 1.52 90phase 273-5 Ex. — 0.000 Sb 0.010 20 amorphous ⊚ 2.4 1.50 90 phase 273-6Ex. — 0.000 O 0.010 19 amorphous ⊚ 2.3 1.52 90 phase 273-7 Ex. — 0.000 N0.010 19 amorphous ⊚ 2.4 1.51 90 phase

Table 7 shows Examples whose M content (a), B content (b), P content(c), Si content (d), and C content (e) were changed. Incidentally, thetype of M was Nb. Examples whose each component content was in apredetermined range had a good resistivity ρ, a good saturation magneticflux density Bs, a good coercivity Hc, and a good permeability μ′.

In Sample No. 211 (M content (a) was too small), the ribbon before theheat treatment was composed of crystalline phases and had a smallresistivity ρ, a significantly large coercivity Hc, a significantlysmall permeability μ′, and no specific frequency f after the heattreatment. Sample No. 220 (M content (a) was too large) had a lowsaturation magnetic flux density Bs.

In Sample No. 221 (B content (a) was too small), the ribbon before theheat treatment was composed of crystalline phases and had a smallresistivity ρ, a significantly large coercivity Hc, a significantlysmall permeability μ′, and no specific frequency f after the heattreatment. Sample No. 228 (B content (a) was too large) had a lowsaturation magnetic flux density Bs.

A comparative example containing no P (c=0) and a comparative examplecontaining no C (e=0) tended to have a small resistivity ρ, a largecoercivity Hc, a small permeability μ′, and a small specific frequency fafter the heat treatment. A comparative example whose C content (e=0)was too large tended to have a low saturation magnetic flux density Bs,a low permeability μ′, and a low specific frequency f.

Sample No. 252 (Si content (d) was too large) had a large saturationmagnetic flux density.

Table 8 shows Examples whose M type in Sample No. 206 was changed.

Table 8 shows that excellent characteristics were exhibited even if thetype of M was changed.

Table 9 shows Examples where a part of Fe in Sample No. 206 wassubstituted by X1 and/or X2.

Table 9 shows that excellent characteristics were exhibited even if apart of Fe was substituted by X1 and/or X2.

Among the samples shown in FIG. 9, it was confirmed that a sample wherea part of Fe was substituted by X2 easily had a soft magnetic alloycontaining no crystalline phases composed of crystals having a grainsize of larger than 30 nm (a soft magnetic alloy according to the secondaspect of the present invention). To facilitate generation ofcrystalline phases composed of crystals having a grain size of largerthan 30 nm, the ribbon to be obtained specifically was controlled tohave a thickness of about 40 nm to 50 μm. Table 10 shows the results.

TABLE 10 Fe (1 − (α + β)) X1αX2β (a to e are the same as those of SampleNo. 206) saturation magnetic flux Comparative X1 X2 ribbon resistivitycoercivity density Sample Example/ α|1 − β|1 − thickness ρ Hc Bs No.Example type (a + b + c + d + e)| type (a + b + c + d + e)| (μm) XRD (μΩ cm) (A/m) (T) 206a Ex. — 0.000 — 0.000 39 amorphous ◯ 1.8 1.56 phase266a Ex. — 0.000 Al 0.010 41 amorphous ⊚ 2.2 1.53 phase 267a Ex. — 0.000Zn 0.010 42 amorphous ⊚ 2.1 1.53 phase 268a Ex. — 0.000 Sn 0.010 44amorphous ⊚ 2.3 1.54 phase 269a Ex. — 0.000 Cu 0.010 43 amorphous ⊚ 2.31.53 phase 271a Ex. — 0.000 Bi 0.010 41 amorphous ⊚ 2.5 1.51 phase 272aEx. — 0.000 La 0.010 44 amorphous ⊚ 2.6 1.52 phase 273a Ex. — 0.000 Y0.010 42 amorphous ⊚ 2.4 1.51 phase 273-2a Ex. — 0.000 Mn 0.010 43amorphous ⊚ 2.4 1.52 phase 273-3a Ex. — 0.000 Ag 0.010 41 amorphous ⊚2.2 1.51 phase 273-4a Ex. — 0.000 As 0.010 40 amorphous ⊚ 2.4 1.52 phase273-5a Ex. — 0.000 Sb 0.010 41 amorphous ⊚ 2.4 1.50 phase 273-6a Ex. —0.000 O 0.010 42 amorphous ⊚ 2.1 1.52 phase 273-7a Ex. — 0.000 N 0.01040 amorphous ⊚ 2.5 1.51 phase

Table 10 shows that a soft magnetic alloy containing no crystallinephases composed of crystals having a grain size of larger than 30 nm wasobtained in each sample of Table 9 even if the ribbon to be obtained hada thickness of about 40 μm to 50 μm.

Experimental Example 6

In Experimental Example 6, the average grain size of the initial finecrystals and the average grain size of the Fe based nanocrystallinealloy in Sample No. 206 were changed by appropriately changing thetemperature of molten metal and the heat-treatment conditions after theribbon was manufactured. Table 11 shows the results. Incidentally, allsamples shown in Table 11 had a good permeability μ′.

TABLE 11 Fe (1 − (a + b + c + d + e) ) MaBbPcSidCe (a to e are the sameas those of Sample No. 206) average average grain size grain size heatheat of Fe based Comparative metal of initial fine treatment treatmentnanocrystalline Sample Example/ temperature crystals temperature timealloy ρ Hc Bs No. Example (° C.) (nm) (° C.) (h.) (nm) XRD (μ Ω cm)(A/m) (T) 274 Ex. 1200 no initial fine 800 1 10 amorphous ◯ 2.0 1.56crystals phase 275 Ex. 1225 0.1 450 1 3 amorphous ◯ 2.4 1.52 phase 276Ex. 1250 0.3 500 1 5 amorphous ◯ 2.1 1.52 phase 277 Ex. 1250 0.3 550 110 amorphous ◯ 2.2 1.51 phase 278 Ex. 1250 0.3 575 1 13 amorphous ◯ 2.11.54 phase 206 Ex. 1250 0.3 600 1 10 amorphous ◯ 1.8 1.56 phase 279 Ex.1275 10 600 1 12 amorphous ◯ 1.8 1.54 phase 280 Ex. 1275 10 650 1 30amorphous ◯ 2.1 1.52 phase 281 Ex. 1300 15 600 1 17 amorphous ◯ 3.1 1.52phase 282 Ex. 1300 15 650 10 50 amorphous ◯ 3.2 1.51 phase

Table 11 shows that when the initial fine crystals had an average grainsize of 0.3 to 10 nm and when the Fe based nanocrystalline alloy had anaverage grain size of 5 to 30 nm, both saturation magnetic flux densityBs and coercivity Hc were good compared to those when these ranges werenot satisfied.

NUMERICAL REFERENCES

-   21, 31 . . . nozzle-   22, 32 . . . molten metal-   23, 33 . . . roller-   24, 34 . . . ribbon-   25, 35 . . . chamber-   26 . . . peel gas spray device

What is claimed is:
 1. A soft magnetic alloy comprising a main componentof(Fe_((1−(α+β)))X1_(α)X2_(β))_((1−(a+b+c+d+)))M_(a)B_(b)P_(c)Si_(d)C_(e),in which X1 is one or more of Co and Ni, X2 is one or more of Al, Mn,Ag, Zn, Sn, As, Sb, Cu, Cr, Bi, N, O, and rare earth elements, M is oneor more of Nb, Hf, Zr, Ta, Mo, W, and V, 0.020≤a≤0.14 is satisfied,0.020<b≤0.20 is satisfied, 0.040<c≤0.15 is satisfied, 0≤d≤0.060 issatisfied, 0≤e≤0.030 is satisfied, α≥0 is satisfied, β≥0 is satisfied,and 0≤α+β≤0.50 is satisfied, wherein the soft magnetic alloy has ananohetero structure where initial fine crystals exist in an amorphousphase.
 2. A soft magnetic alloy comprising a main component of(Fe_((1−(α+β)))X1_(α)X2_(β))_((1−(a+b+c+d+e)))M_(a)B_(b)P_(c)Si_(d)C_(e),in which X1 is one or more of Co and Ni, X2 is one or more of Al, Mn,Ag, Zn, Sn, As, Sb, Cu, Cr, Bi, N, O, and rare earth elements, M is oneor more of Nb, Hf, Zr, Ta, Mo, W, and V, 0.020≤a≤0.14 is satisfied,0.020<b≤0.20 is satisfied, 0<c≤≤0.040 is satisfied, 0≤d≤0.060 issatisfied, 0.0005<e<0.0050 is satisfied, α≥0 is satisfied, β≥0 issatisfied, and 0≤α+β≤0.50 is satisfied, wherein the soft magnetic alloyhas a nanohetero structure where initial fine crystals exist in anamorphous phase.
 3. The soft magnetic alloy according to claim 1,wherein the initial fine crystals have an average grain size of 0.3 to10 nm.
 4. The soft magnetic alloy according to claim 2, wherein theinitial fine crystals have an average grain size of 0.3 to 10 nm.
 5. Asoft magnetic alloy comprising a main component of(Fe_((1−(α+β)))X1_(α)X2_(β))_((1−(a+b+c+d+e)))M_(a)B_(b)P_(c)Si_(d)C_(e),in which X1 is one or more of Co and Ni, X2 is one or more of Al, Mn,Ag, Zn, Sn, As, Sb, Cu, Cr, Bi, N, O, and rare earth elements, M is oneor more of Nb, Hf, Zr, Ta, Mo, W, and V, 0.020≤a≤0.14 is satisfied,0.020<b≤0.20 is satisfied, 0.040<c≤0.15 is satisfied, 0≤d≤0.060 issatisfied, 0≤e≤0.030 is satisfied, α≥0 is satisfied, β≥0 is satisfied,and 0≤α+β≤0.5 is satisfied, wherein the soft magnetic alloy has astructure of Fe based nanocrystallines.
 6. A soft magnetic alloycomprising a main component of(Fe_((1−(α+β)))X1_(α)X2_(β))_((1−(a+b+c+d+e)))M_(a)B_(b)P_(c)Si_(d)C_(e),in which X1 is one or more of Co and Ni, X2 is one or more of Al, Mn,Ag, Zn, Sn, As, Sb, Cu, Cr, Bi, N, O, and rare earth elements, M is oneor more of Nb, Hf, Zr, Ta, Mo, W, and V, 0.020≤a≤0.14 is satisfied,0.020<b≤0.20 is satisfied, 0<c≤0.040 is satisfied, 0≤d≤0.060 issatisfied, 0.0005<e<0.0050 is satisfied, α≥0 is satisfied, β≥0 issatisfied, and 0≤α+β≤0.50 is satisfied, wherein the soft magnetic alloyhas a structure of Fe based nanocrystallines.
 7. The soft magnetic alloyaccording to claim 5, wherein the Fe based nanocrystallines have anaverage grain size of 5 to 30 nm.
 8. The soft magnetic alloy accordingto claim 6, wherein the Fe based nanocrystallines have an average grainsize of 5 to 30 nm.
 9. The soft magnetic alloy according to claim 5,wherein 0.73≤1−(a+b+c+d+e)≤0.95 is satisfied.
 10. The soft magneticalloy according to claim 5, wherein 0≤α{1−(a+b+c+d+e)}≤0.40 issatisfied.
 11. The soft magnetic alloy according to claim 5, wherein α=0is satisfied.
 12. The soft magnetic alloy according to claim 5, wherein0≤β{1−(a+b+c+d+e)}≤0.030 is satisfied.
 13. The soft magnetic alloyaccording to claim 5, wherein β=0 is satisfied.
 14. The soft magneticalloy according to claim 5, wherein α=β=0 is satisfied.
 15. The softmagnetic alloy according to claim 5, comprising a ribbon shape.
 16. Thesoft magnetic alloy according to claim 5, comprising a powder shape. 17.A magnetic device comprising the soft magnetic alloy according toclaim
 1. 18. A magnetic device comprising the soft magnetic alloyaccording to claim
 2. 19. A magnetic device comprising the soft magneticalloy according to claim
 5. 20. A magnetic device comprising the softmagnetic alloy according to claim 6.